CN1241115A - Insecticidal and miticidal compositions - Google Patents
Insecticidal and miticidal compositions Download PDFInfo
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- CN1241115A CN1241115A CN97180397A CN97180397A CN1241115A CN 1241115 A CN1241115 A CN 1241115A CN 97180397 A CN97180397 A CN 97180397A CN 97180397 A CN97180397 A CN 97180397A CN 1241115 A CN1241115 A CN 1241115A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
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Abstract
The invention relates to an insecticidal and miticidal composition which contains as active ingredients chlorfenapyr (4-bromo-2-(4-chlorophenyl) 1-(ethoxymethyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile in combination with one or more compounds selected from the organophosphoric acid ester-type compounds represented by general formulae (I) or (II), wherein X represents oxygen or sulfur atom, Y represents oxygen or sulfur atom, group or single bond represented by -S(CH2)nS- (n is 1 or 2), R<1> represents C1-C6 alkyl group, R<2> represents C1-C8 alkoxy group, C1-C8 alkylthio group, C1-C4 alkylcarbonylamino group, C1-C6 alkylamino group or phenyl group, and R<3> represents C1-C8 alkyl group, C2-C6 alkenyl group, amino group, phenyl group, or heteroaryl group, which are substituted by 1 to 4 same or different substituents selected from the substituent group A mentioned below or formula (III) (wherein R<1>, R<2> and X mean the same as the above-mentioned) or unsubstituted. Substituent group A: C1-C8 alkyl group, C1-C8 alkoxy group, C1-C6 aliphatic acyl group, C1-C6 alkoxy-carbonyl group, C1-C6 alkylthio group, C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C4 alkylsulfinyl group, C1-C4 haloalkyl group, N-C1-C4 alkylcarbamoyl group, N,N-di-C1-C4 alkylcarbamoyl group, N-C1-C4 alkyl-N-formylcarbamoyl group, heteroaryl group which may be substituted, phenyl group which may be substituted, halogen atom, nitro group, cyano group, hydroxy group and acetylamino group. The insecticidal and miticidal composition of the invention is effective against pests and mites having resistance to commercial insecticidal and miticidal agents.
Description
Invention field
The present invention relates to a kind of insecticide acaricide composition that can use in the agriculture and garden field effectively.More particularly, relate to and a kind ofly contain more than two kinds active component and can prevent and treat the insecticide acaricide composition that commercial insecticidal/acaricidal agent is produced chemical sproof insect and mite especially effectively.
Background of invention
Control is included, but is not limited to insect to active component 4-bromo-2-(4-chlorphenyl)-1-ethoxymethyl-5-(trifluoromethyl) pyrroles-3-formonitrile HCN of known insecticide acaricide composition of the present invention (to call the fragrant pyrrole (chlorfenapyr) of chlorine in the following text) and mite is effective interior insect: leafhopper Semiptera insects such as (Doltocephalidae), diamond-back moth (Plutella xylostella), ash wing sugar moth (Spodoptera litura) and apple leaf miner lepidoptera pests such as (Phyllonorycter ringoniella), palm thrips (Thrips palmi) and tea golden thistle horse thrips insects such as (Spirtothrips dorsalis), also has the insect on the agriculture and garden, as cotton spider mites (Tetranychus urticae koch), kamisawa tetranychus (Tetranychus kanzawai kishida) and tangerine rust mite mite classes such as (Aculops pelekassi) (the open communique of Japan's special permission 1989 No. 104042).
Second active component of insecticide acaricide composition of the present invention comprises one or more organophosphorus ester compounds, and known these organophosphorus ester compounds are can prevent and treat the insecticidal/acaricidal agent of the insect (as Semiptera, Lepidoptera and coleopteron and mite) on the agricultural effectively and the control paddy rice is withered and the fungicide of soil-borne disease.
Though for the various insects of control (as insect on the agriculture and garden or the insect harmful to health) have been developed many insecticidal/acaricidal agents, and be used alone or as a mixture in practice, but the result who reuses these medicaments is that insect has produced drug resistance to various medicaments.
Particularly, important economic insects (as easily insecticide being produced chemical sproof tetranychid (Tetranychidae) because it has the ability of laying eggs in a large number and producing a large amount of offsprings) only needs a few days to produce drug resistance and is just causing very big concern on agriculture and garden.The generation of drug resistance in these insect offsprings also is under the help of its higher mutation rate and by the seldom inbreeding that causes of migration.Owing to these reasons, cotton spider mites (Tetranychusurticae koch), kamisawa tetranychus (Tetranychus kanzawai kishida) and tangerine rust mite (Aculopspelekassi) etc. have produced drug resistance to nearly all existing insecticide to a certain extent.Therefore, for preventing and controlling the infringement that causes by tetranychid, be starved of a kind of new insecticidal/acaricidal agent of exploitation and existing miticide produced chemical sproof tetranychid efficiently to kill those.
Yet, obtain a kind of to existing insecticidal/acaricidal agent do not have mutual drug resistance and do not have toxicity, be unusual difficulty to the little insecticide acaricide composition of the negative effect of environment.Therefore, people are seeking a kind of method that can postpone or prevent insect kind formation resistant strain always.For the term of validity that makes the medicament of using is long as much as possible, adopt method that samsara uses the medicament with different mechanism of action in practice with Pest Control effectively.But this method might not produce good effect.Therefore, after the drug resistance problem occurring, studied by insecticide and miticide are mixed and eliminated chemical sproof countermeasure.Yet, do not find high synergistic effect always.
Therefore, the objective of the invention is, a kind of insecticide acaricide composition is provided, even for the fragrant pyrrole of chlorine being produced chemical sproof tetranychid, it also can show good control efficiency.Brief summary of the invention
Eliminate its chemical sproof countermeasure for establishing a kind of chemical sproof problem before occurring at tetranychid fragrant pyrrole to chlorine, studied the synergistic effect of existing insecticide, miticide and fungicide with resistant strain, described resistant strain is to set up by the tetranychid of handling with the fragrant pyrrole of chlorine is carried out artificially breeding in the laboratory.Therefore, have found that, contain as fragrant pyrrole of the chlorine of active component and at least a selected organophosphorus ester compound insecticide acaricide composition can show that synergy is a synergistic effect, and this effect or effect can't be predicted from the independent result of use of each single composition.The detailed description of invention
Insecticide acaricide composition of the present invention is effective especially to control tetranychid (as cotton spider mites (Tetranychus urticae koch), tetranychus telarius (Tetranychus cinnabarinus), kamisawa tetranychus (Tetranychus kanzawai kishida) and tetranychus viennensis (Tetranychus viennensis zacher) etc.).
Advantageously, insecticide acaricide composition of the present invention not only has extremely mite synergistic effect to above-mentioned tetranychid, but also can prevent and treat fruit tree (for example oranges and tangerines, apple and pear simultaneously; Tea tree; Vegetables etc.) thorny insect on the important agricultural crops such as is as leaf roller (Tortricidae), fruit moth (Carposinidae), lyonetid (Lyonetiidae), wood louse (Pentatomidae), aphid (Aphididae), leafhopper (Deltociphalidae), ladybug (Coccinea), thrips (Thripidae), diamond-back moth (Plutellaxylostella), cabbage army worm (Mamestra brassicae), chrysomelid (Chrysomelidae), orange aleyrodid (Aleyrodidae) etc.
The fragrant pyrrole of the active component chlorine of insecticide acaricide composition of the present invention is to see the compound known that is set forth in the open communique of Japan's special permission 1989 No. 104042, and its using method as the insecticidal/acaricidal agent on the agriculture and garden also has description in this communique.It also can easily synthesize according to the method for describing in this communique.
The organophosphorus ester compound that is suitable as second active component in the present composition be general formula (I) or (II) expression compound.
In the formula,
X represents oxygen atom or sulphur atom,
Y represent oxygen atom or sulphur atom ,-S (CH
2)
nGroup that S-represents (n is 1 or 2) or singly-bound,
R
1Expression C
1-C
6Alkyl,
R
2Expression C
1-C
8Alkoxyl, C
1-C
8Alkylthio group, C
1-C
4Alkyl-carbonyl-amino, C
1-C
6Alkylamino or phenyl,
R
3Expression C
1-C
8Alkyl, C
2-C
6Alkenyl, amino, phenyl or the heteroaryl that is replaced by 1 to 4 identical or different substituting group that is selected from the following A group, or following formula (III)
(in the formula, R
1, R
2The same with the definition of X)
Substituent A: C
1-C
8Alkyl, C
1-C
8Alkoxyl, C
1-C
6Aliphatic acyl, C
1-C
6Alkoxy carbonyl, C
1-C
6Alkylthio group, C
1-C
6Alkylamino, two C
1-C
6Alkyl amino, C
1-C
4Alkyl sulphinyl, C
1-C
4Haloalkyl, N-C
1-C
4Alkyl-carbamoyl, N, N-two C
1-C
4Alkyl-carbamoyl, N-C
1-C
4Alkyl-N-formoxyl carbamoyl, can substituted heteroaryl, can substituted phenyl, halogen atom, nitro, cyano group, hydroxyl and acetylamino.
At general formula (I) with (III), R
1" C in the definition
1-C
6Alkyl " expression has the straight or branched alkyl of 1-6 carbon atom; as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, 2-methyl butyl, neopentyl, 1-ethyl-propyl group, n-hexyl, 4-methyl amyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, 3; 3-dimethylbutyl, 2; 2-dimethylbutyl, 1; 1-dimethylbutyl, 1; 2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl and 2-ethyl-butyl.
At general formula (I) with (IIII), R
2" C in the definition
1-C
8Alkoxyl " expression has the straight or branched alkoxyl of 1-8 carbon atom; as methoxyl group; ethyoxyl; positive propoxy; isopropoxy; n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, 2-methyl butoxy, neopentyl oxygen, just own oxygen base, 4-methyl amoxy, 3-methyl amoxy, 2-methyl amoxy, 3,3-dimethyl butoxy, 2,2-dimethyl butoxy, 1,1-dimethyl butoxy, 1,2-dimethyl butoxy, 1,3-dimethyl butoxy, 2,3-dimethyl butoxy, positive heptan oxygen base and n-octyloxy.
R
2" C in the definition
1-C
8Alkylthio group " expression has the straight or branched alkylthio group of 1-8 carbon atom, as methyl mercapto, ethylmercapto group, positive rosickyite base, different rosickyite base, positive butylthio, positive penta sulfenyl, just own sulfenyl, just heptan sulfenyl and positive hot sulfenyl.
R
2" C in the definition
1-C
4Alkyl carbonyl amino " represent the carbonylamino that combines with straight or branched alkyl with 1-4 carbon atom, as first carbonylamino, B carbonyl amino, positive third carbonylamino, isopropyl carbonyl amino, positive fourth carbonylamino, Zhong Ding carbonylamino and uncle's fourth carbonylamino.
R
2" C in the definition
1-C
6Alkylamino " represent the amino that combines with straight or branched alkyl with 1-6 carbon atom, as methylamino, ethylamino, n-propylamine base, isopropylamino, n-butyl amine base, isobutyl amino, Zhong Ding amino, uncle's fourth amino, pentylamine base with just oneself is being amino.
At general formula (I) with (II), R
3With " the C in the substituent A definition
1-C
8Alkyl " expression has the straight or branched alkyl of 1-8 carbon atom; as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, 2-methyl butyl, neopentyl, 1-ethyl-propyl group, n-hexyl, 4-methyl amyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, 3; 3-dimethylbutyl, 2; 2-dimethylbutyl, 1; 1-dimethylbutyl, 1; 2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl and 2-ethyl-butyl, n-heptyl and n-octyl.
R
3" C in the definition
2-C
6Alkenyl " expression has the straight or branched alkenyl of 2-6 carbon atom, as vinyl; the 1-acrylic; the 2-acrylic; 1-methyl-2-acrylic; 2-methyl isophthalic acid-acrylic; 2-methyl-2-acrylic, 2-ethyl-2-acrylic, the 1-cyclobutenyl, the 2-cyclobutenyl, 1-methyl-2-butene base, 2-methyl-2-butene base, 3-methyl-2-butene base, 1-ethyl-2-cyclobutenyl, the 3-cyclobutenyl, 1-methyl-3-cyclobutenyl, 2-methyl-3-cyclobutenyl, 1-ethyl-3-cyclobutenyl, the 1-pentenyl, the 2-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, the 3-pentenyl, 1-methyl 3-pentenyl, 2-methyl-3-pentenyl, the 4-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, the 1-hexenyl, the 2-hexenyl, the 3-hexenyl, 4-hexenyl and 5-hexenyl.
R
3With 5 to the 8 yuan of heterocyclic groups of " heteroaryl " expression in the substituent A definition, it can condense, contain 1-5 the identical or different atom that is selected from oxygen atom, sulphur atom and nitrogen-atoms, its example has furyl, thienyl, pyrrolidinyl, oxazolyl, isoxazolyl, thiazolyl, thienyl (thianyl), pyridine radicals, pyridazinyl, pyrazolyl, imidazole radicals, triazinyl, thiadiazolyl group, Imidazothiazole base, benzoisoxazole base, benzopyranyl, quinolyl, benzo thienyl (benzothianyl), Kui oxazolinyl and BTA base.
" C in the substituent A definition
1-C
8Alkoxyl " expression has the straight or branched alkoxyl of 1-8 carbon atom; as methoxyl group; ethyoxyl; positive propoxy; isopropoxy; n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, 2-methyl butoxy, neopentyl oxygen, just own oxygen base, 4-methyl amoxy, 3-methyl amoxy, 2-methyl amoxy, 3,3-dimethyl butoxy, 2,2-dimethyl butoxy, 1,1-dimethyl butoxy, 1,2-dimethyl butoxy, 1,3-dimethyl butoxy, 2,3-dimethyl butoxy, positive heptan oxygen base and n-octyloxy.
" C in the substituent A definition
1-C
6Aliphatic acyl " represent that total carbon atom number is 1-6 a straight or branched aliphatic acyl, as formoxyl, acetyl group, propiono, bytyry and valeryl.
" C in the substituent A definition
1-C
6Alkoxy carbonyl " represent the carbonyl that combines with straight or branched alkoxyl with 1-6 carbon atom, as methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, n-butoxy carbonyl, isobutoxy carbonyl, tert-butoxycarbonyl, n-pentyloxy carbonyl and positive hexyloxy carbonyl.
" C in the substituent A definition
1-C
6Alkylthio group " expression has the straight or branched alkylthio group of 1-6 carbon atom, as methyl mercapto, ethylmercapto group, positive rosickyite base, different rosickyite base, just butylthio, isobutyl sulfenyl, secondary butylthio, uncle's butylthio, positive penta sulfenyl and just own sulfenyl.
" C in the substituent A definition
1-C
6Alkylamino " represent the amino that combines with straight or branched alkyl with 1-6 carbon atom, as methylamino, ethylamino, n-propylamine base, isopropylamino, n-butyl amine base, isobutyl amino, Zhong Ding amino, uncle's fourth amino, pentylamine base with just oneself is being amino.
" two C in the substituent A definition
1-C
6Alkyl amino " amino that combines with two identical or different straight or branched alkyl that contain 1-6 carbon atom of expression, as dimethylamino, diethylamino, methyl ethylamino, dipropyl amino and dibutylamino.
" C in the substituent A definition
1-C
4Alkyl sulphinyl " represent the sulfinyl that combines with straight or branched alkyl with 1-4 carbon atom, as methylsulfinyl, ethyl sulfinyl, n-pro-pyl sulfinyl, isopropyl sulfinyl, normal-butyl sulfinyl, isobutyl group sulfinyl, sec-butyl sulfinyl and tert-butyl group sulfinyl.
" C in the substituent A definition
1-C
4Haloalkyl " expression has the straight or branched haloalkyl of 1-4 carbon atom, as methyl fluoride, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, two bromomethyls, trifluoromethyl, trichloromethyl, 2-fluoro ethyl, 2-chloroethyl, 2-bromoethyl, 2,2; 2-trifluoroethyl, 3-fluoropropyl, 3-chloropropyl, 3-bromopropyl, 2,2,3; 3,3-five fluoropropyls, 2,2; 2-three fluoro-1-methyl-ethyls, 4-fluorine butyl, 4-chlorobutyl, 4-brombutyl and 2; 2,3,3; 4,4-hexafluoro butyl.
" N-C in the substituent A definition
1-C
4Alkyl-carbamoyl " represent the carbamoyl that combines with straight or branched alkyl with 1-4 carbon atom, as N-methylamino formoxyl, N-ethylamino formoxyl, N-n-pro-pyl carbamoyl, N-isopropyl carbamoyl, N-normal-butyl carbamoyl, N-isobutylamino formoxyl, N-sec-butyl carbamoyl and N-tert-butyl group carbamoyl.
" N, N-two C in the substituent A definition
1-C
4Alkyl-carbamoyl " carbamoyl that combines with two identical or different straight or branched alkyl that contain 1-6 carbon atom of expression; as N; N-formyl-dimethylamino, N, N-diethylamino formoxyl, N-ethyl-N-methylamino formoxyl, N-methyl-N-propyl group carbamoyl and N-isopropyl-N-methylamino formoxyl.
" N-C in the substituent A definition
1-C
4Alkyl-N-formoxyl carbamoyl " represent the formoxyl carbamoyl that combines with straight or branched alkyl with 1-4 carbon atom, as N-formoxyl-N-methylamino formoxyl, N-ethyl-N-formoxyl carbamoyl, N-formoxyl-N-n-pro-pyl carbamoyl, N-formoxyl-N-isopropyl carbamoyl, N-formoxyl-N-normal-butyl carbamoyl, N-formoxyl-N-isobutylamino formoxyl, N-formoxyl-N-sec-butyl carbamoyl and N-formoxyl-N-tert-butyl group carbamoyl.
The example of " halogen atom " in the substituent A definition has fluorine atom, chlorine atom, bromine atoms and iodine atom.
Be the popular name (generic name) and the chemical name of the organophosphorus ester compound listed as illustration below.But these examples are not to be limiting the scope of the invention.Popular name chemical name BRP:O, O-dimethyl-1,2-two bromo-2,2-dichloro-ethyl phosphonic acid ester CVMP:(Z)-2-chloro-1-(2,4, the 5-trichlorophenyl) vinyl-dimethyl base
Phosphate CVP:2-chloro-1-(2, the 4-dichlorophenyl) vinyl diethyl phosphate CYAP:O-4-cyano-phenyl O, O-dimethyl disulfide phosphorothioate DDVP:2,2-dichlorovinyl dimethyl phosphate DEP: dimethyl 2,2,2-three chloro-1-hydroxyethyl phosphonate ester DMTP:S-2,3-dihydro-5-methoxyl group-2-oxo-1,3, the 4-thiadiazoles-
3-ylmethyl O, O-Methyl disulfide substituted phosphate EPN:O-ethyl O-4-nitrobenzophenone thionic phosphonic acids phenyl ester ESP:S-2-ethyl sulfinyl-1-Methylethyl O, O-dimethyl thiol phosphorus
Acid esters IBP:S-benzyl O; O-diisopropyl thiophosphate MEP:O; O-dimethyl O-4-nitro--tolyl phosphorothionate MPP:O; O-dimethyl O-4-methyl mercapto--tolyl phosphorothionate PAP:S-α-ethoxy carbonyl benzyl O; O-Methyl disulfide substituted phosphate PMP:O; O-dimethyl S-phthalimide ylmethyl phosphorodithioate orthene: O; S-dimethyl-N-acetyl group thio-phosphamide Zhi oxazole phosphorus: O; O-diethyl O-5-phenyl-isoxazole azoles-3-base phosphorothionate isofenphos: O-ethyl O-2-isopropoxy carbonyl phenyl N-isopropylthio phosphamide ethion: O; O; O '; O '-tetraethyl S; S '-di-2-ethylhexylphosphine oxide (phosphorodithioate) disulfoton: O; O-diethyl S-2-ethylmercapto group diethyldithioposphoric acid ester etrimfos: O-6-ethyoxyl-2-ethyl-pyrimidine-4-base O, the O-dimethyl disulfide pursues
Phosphate quinalphos: O, O-diethyl O-quinoxaline-2-base phosphorothionate chlopyrifos: O, O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothionate chlorpyrifos-methyl: O, O-dimethyl O-3,5,6-trichloro-2-pyridyl phosphorothionate salithion: 2-methoxyl group-4 (H)-1,3,2 λ
5-benzo two oxa-s phosphorus-2-sulfuration
Thing dimethylvinphos: O-(2-chloro-1-(2 ', 4 '-dichlorophenyl) vinyl)-O, O
-dimethyl phosphate Rogor: O, O-dimethyl S-methylamino formyl methyl phosphorodithioate first Toyodan: O-ethyl O-4-(methyl mercapto) phenyl S-propyl disulfide substituted phosphate diazinon: O, O-diethyl O-2-isopropyl-6-methylpyrimidine-4-base thionic
Phosphate thiometon: S-2-ethylmercapto group O, O-Methyl disulfide substituted phosphate Kilval: O, O-dimethyl-S-2-(1-methylamino formyl ethylmercapto group) ethyl
Thiolophosphate pyraclofos: (RS)-(O-1-(4-chlorphenyl) pyrazoles-4-yl) O-
Ethyl S-propyl group thiolophosphate pyridaphethione: O, and O-diethyl O-(2,3-dihydro-3-oxo-2-phenyl-6
-pyridazinyl) phosphorothionate pirimiphos-methyl: O-2-diethylin-6-methylpyrimidine-4-base O, O-dimethyl disulfide
Phosphorothioate Toyodan: O-(2,4 dichloro benzene base) O-ethyl S-propyl disulfide substituted phosphate Kayaphos: 4-(methyl mercapto) phenyl dipropyl phosphate
Profenofos: O-4-bromo-2-chlorphenyl O-ethyl S-propyl group thiolophosphate
Phosalone: S-6-chloro-2,3-dihydro-2-oxo--1,3-benzoxazole-3-
Ylmethyl O, the O-diethyl phosphorothioate
The peace fruit: S-(formyl (methyl) carbamoyl methyl) O, the O-Methyl disulfide is for phosphorus
Acid esters
Malathion: S-1, two (ethoxy carbonyl) ethyl O of 2-, the O-Methyl disulfide is for phosphoric acid
Ester
Nuvacron: dimethyl (E)-1-methyl-2-(methylamino formyl) vinyl phosphorus
Acid esters
The above-mentioned title of insecticide and fungicide is the popular name of seeing " SHIBUYA INDEX-1996-(the 7th edition) " that be set forth in " agricultural chemicals handbook 1992 editions " that Japanese plant protection association (Japan PlantProtection Association) published on July 30th, 1992 and the publication on April 1st, 1996 of complete agricultural (ZENNOH) association.
In the present invention, in above-mentioned insecticide and fungicide, especially preferred O-4-cyano-phenyl O, O-dimethyl disulfide phosphorothioate (CYAP), O-ethyl O-4-nitrobenzophenone thionic phosphonic acids phenyl ester (EPN), S-benzyl O, O-diisopropyl thiophosphate (IBP), O, O-dimethyl O-4-nitro--tolyl phosphorothionate (MEP), O, O-dimethyl O-4-methyl mercapto--tolyl phosphorothionate (MPP), S-α-ethoxy carbonyl benzyl O, O-Methyl disulfide substituted phosphate (PAP), O, O, O ', O '-tetraethyl S, S '-di-2-ethylhexylphosphine oxide (phosphorodithioate) (ethion), O, O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothionate (chlopyrifos), O, O-dimethyl O-3,5,6-trichloro-2-pyridyl phosphorothionate (chlorpyrifos-methyl), O-ethyl O-4-(methyl mercapto) phenyl S-propyl disulfide substituted phosphate (first Toyodan), O, O-diethyl O-2-isopropyl-6-methylpyrimidine-4-base phosphorothionate (diazinon), O, O-diethyl O-(2,3-dihydro-3-oxo-2-phenyl-6-pyridazinyl) phosphorothionate (pyridaphethione), O-(2, the 4-dichlorophenyl) O-ethyl S-propyl disulfide substituted phosphate (Toyodan), S-6-chloro-2,3-dihydro-2-oxo--1,3-benzoxazole-3-ylmethyl O, O-diethyl phosphorothioate (Phosalone), S-1, two (ethoxy carbonyl) ethyl O of 2-, O-Methyl disulfide substituted phosphate (malathion) is because they have good synergistic effect with chlorine sweet smell pyrrole.
For preparing insecticide acaricide composition of the present invention, should pass through existing method (as fragrant pyrrole of chlorine and organophosphorus ester compound are mixed with suitable carriers and assistant agent (as emulsifier, dispersant, stabilizing agent, suspending agent, bleeding agent etc.)) it is mixed with wetting powder, water-based concentrate, emulsion, concentrate, colloidal sol (flowable), pulvis, aerosol etc.
The total content of active component (% represents with weight) should account for about about 1-90% of wetting powder, water-based concentrate, emulsion, concentrate and sol preparation in the present composition.Be preferably, the total content of active component accounts for the 0.5-10% of pulvis, about 0.01-2% of aerosol preparations.
The carrier that is adapted at using in the insecticide acaricide composition of the present invention can be to be generally used for any solid or the liquid-carrier of agriculture and garden with composition.Optionally, can use various surfactants, stabilizing agent and other assistant agent composition.
In the preparation of commerce usefulness, composition of the present invention can also be the mixture with other active component (for example various insecticides, miticide, fungicide and weed killer herbicide, plant growth regulator, repellant, attractant, synergist, fertilizer and aromatic), to expand its applicability.
When the ratio of the fragrant pyrrole of chlorine and organophosphorus ester compound was 1 weight portion with the fragrant pyrrole of chlorine in the insecticide acaricide composition of the present invention, organophosphorus ester compound was about the 0.01-100 weight portion, is about the 0.5-20 weight portion preferably.
Though the visual essential condition of amount of application (as the kind of population density, target crop and cropping pattern, weather condition, method of application etc.) and different, but generally speaking, the total amount of fragrant pyrrole of per 10 ares of chlorine of using and organophosphorus ester compound is about 0.1-1, and 000g is about 20-500g preferably.In practice, when the present composition was wetting powder, water-based concentrate, emulsion, concentrate, colloidal sol etc., dilutable water and the ratio of using that rises with per 10 ares of about 100-700 were applied on the crop.When composition of the present invention is mixed with pulvis or aerosol, crop can be handled with undiluted preparation.
In the following embodiments insecticide acaricide composition of the present invention is further described.But these embodiment are not limiting the scope of the invention.All parts all by weight.
Embodiment 1 example of formulations 1: 10 parts of (trade names of the fragrant 20 parts of Sorpol 3005X of 25 parts of dimethyl formamides of 40 parts of dimethylbenzene of 5 parts of CYAP of pyrrole of emulsion chlorine, the polyoxyethylene-type surfactant that Dong Bang KCC produces) mentioned component is mixed equably and dissolve, obtain emulsion.
Embodiment 2 example of formulations 2: 15 parts of (trade names of the fragrant 50 parts of Carplex #80 of 5 parts of PAP of pyrrole of wetting powder chlorine, the white carbon that the wild adopted Co., Ltd. of salt produces) 22 parts of (trade names of Zeeklite SP, kaolin that Zeeklite industrial group produces and the mixture of cerite (cericite)) 8 parts of Lignosites mix mentioned component equably with the airbrasive machine, obtain wetting powder.
Embodiment 3 example of formulations 3: colloidal sol (flowable)
5 parts of the fragrant pyrroles of chlorine
25 parts of chlorpyrifos-methyls
8 parts of ethylene glycol
5 parts of Sorpol AC3020
(trade name, Dong Bang KCC product)
0.1 part of xanthans
56.9 parts in water
Ethylene glycol, the Sorpol AC3020 of the fragrant pyrrole of chlorine, chlorpyrifos-methyl and preparation in advance fully mixed in water with the mixture of xanthans and disperse.With this slip Dynomill (grinder, ShinmaruEnterprises Co., Ltd. product) wet method abrasive dust, obtain colloidal sol (flowable) then.
Embodiment 4 example of formulations 4: 91 parts of 5 parts of clays of the fragrant 3.5 parts of white carbons of 0.5 part of MEP of pyrrole of pulvis chlorine (Japanese talcum Co., Ltd. product) mix mentioned component equably and pulverize, and obtain pulvis.Each preparation that makes above is suitable as agricultural chemicals.
Embodiment 5 experimental example 1
In this experiment, carried out the evaluation of miticidal effect with female insect with fragrant chemical sproof kamisawa tetranychus of pyrrole of chlorine (Tetranychus kanzawaikishida).
Downcut roundleaf sheet (diameter 2cm) from early years of Kidney bean with the knife-edge card punch, 4 blades are placed on the wet cotton wool in the plastic cup (diameter 8cm).On each blade, inoculate 4 and the fragrant pyrrole of chlorine has been produced strong chemical sproof kamisawa tetranychus (Tetranychus kanzawai kishida) female insect.
After the inoculation, be dispersed in the water that contains 200ppm expander (Sorpol3005X) fragrant pyrrole of chlorine and organophosphorus ester compound and dilution, make active component reach predetermined concentration.In each plastic cup, spray the 3.5ml test solution and each plastic cup is preserved in 25 ± 1 ℃ thermostatic chamber (each concentration is tried worms with 32 tests with rotating spraying tower (auspicious fringe science Co., Ltd. product), each preparation is estimated with 4-5 kind concentration, and each repeats 2 times).Handled the back the 2nd, to the survival number of the female insect that obtains the fragrant chemical sproof kamisawa tetranychus of pyrrole of very strong chlorine (Tetranychus kanzawai kishida) with death toll is counted and calculate lethality (%) according to following formula.
Use these data, obtain LC by existing probable value analytical technology
50Value.Calculate common toxic factor with the Sun and Johnson formula that is commonly used to determine synergistic activity (J.Econ.Ent., Vol53, p.887,1960).
The LC of each active ingredient in the insecticide acaricide composition of the present invention
50Value sees Table 1.The LC of the present composition
50Value and common toxic factor see Table 2.
Toxic factor=T ° altogether
When T ° of value greater than 100 the time, numerical value is big more, the expression synergistic effect is strong more.When T ° of value equaled 100, expression had addition.When T ° of value less than 100 the time, numerical value is more little, the expression antagonism is big more.Toxic factor is for a more detailed description altogether to calculating with Sun and Johnson formula below.
To test-compound A (independent), test-compound B (independent) and the mixture M (LC of compd A+B)
50Value is measured.
Actual poison exponent=the M of mixture M
Ti
Each LC with effective constituents A and B
50The LC of value and A+B mixture
50Value is determined the actual poison exponent shown in the following formula.
The theoretical poison exponent of mixture M=theoretical M
Ti
Theoretical M
Ti=(%B among the poison exponent * M of the %A+B among poison exponent * M of A)
Poison exponent=B of B
Ti 
Poison exponent=A of A
Ti
A
ti＝100
Table 1 test-compound is to the evaluation of effect with the chemical sproof kamisawa tetranychus female insect of the fragrant pyrrole of chlorine
Test-compound LC
50(ppm)
The fragrant pyrrole 1500 of chlorine
CYAP 3200
EPN 3100
IBP 1300
MEP 3200
MPP 1100
PAP 2000
Ethion 3100
Chlopyrifos 3200
Chlorpyrifos-methyl 790
First Toyodan 320
Diazinon 3200
Pyridaphethione 1900
Toyodan 260
Phosalone 350
Malathion 3400
The examination mite is by the kamisawa tetranychus colony that traps is carried out the female insect of the long-term kamisawa tetranychus resistant strain that the chemical sproof artificially breeding of the fragrant pyrrole of chlorine is obtained in the laboratory from the field.Because the fragrant pyrrole of chlorine is to the LC of tetranychid sensitive strain
50Value is about 5ppm, and therefore, this strain has improved about 300 times to the drug resistance of the fragrant pyrrole of chlorine.
Because this kamisawa tetranychus has obtained the chemical sproof colony to organophosphorus ester when coming leisure to trap from the field, therefore, all organophosphorus esters that tried only have faint acaricidal action.
Table 2 is tried the evaluation of mixture to effect with the chemical sproof kamisawa tetranychus female insect of the fragrant pyrrole of chlorine
Tried mixing rate (the fragrant pyrrole of chlorine: LC other composition)
50(ppm) T
c
Fragrant pyrrole+the CYAP of chlorine 1: 8 120 920
Fragrant pyrrole+the EPN of chlorine 1: 9 300 930
Fragrant pyrrole+the IBP of chlorine 1: 12 460 290
Fragrant pyrrole+the MEP of chlorine 1: 11 130 2300
Fragrant pyrrole+the MPP of chlorine 1: 10 290 390
Fragrant pyrrole+the PAP of chlorine 1: 10 180 1100
Fragrant pyrrole+the ethion of chlorine 1: 10 120 2400
Fragrant pyrrole+the chlopyrifos of chlorine 1: 8 220 1300
Fragrant pyrrole+the chlorpyrifos-methyl of chlorine 1: 5 97 880
The fragrant pyrrole of chlorine+first Toyodan 3: 20 170 210
Fragrant pyrrole+the diazinon of chlorine 5: 34 430 650
Fragrant pyrrole+the pyridaphethione of chlorine 1: 10 340 550
Fragrant pyrrole+the Toyodan of chlorine 1: 9 100 280
Fragrant pyrrole+the Phosalone of chlorine 1: 7 180 220
Fragrant pyrrole+the malathion of chlorine 1: 10 370 820
From the data of table 2 as can be known, the common toxic factor that is tried mixture is more than 100, and this shows between fragrant pyrrole of chlorine and the organophosphorus ester compound very strong synergistic effect.Though the detailed mechanism of the synergistic effect of the present composition it be unclear that, estimate it is to have obtained due to metabolism system (enzyme group) that the chemical sproof tetranychid of the fragrant pyrrole of chlorine carries out detoxification and decomposition with the fragrant pyrrole of chlorine suppressed by organophosphorus ester compound.Therefore, should be understood that second composition in the insecticide acaricide composition of the present invention is not limited in organophosphorus ester compound and the top specifically described organophosphorus ester compound that is tried in the foregoing description.
Claims (8)
1. insecticide acaricide composition, it contains as fragrant pyrrole of the chlorine of active component and at least a or multiple general formula (I) or (II) organophosphorus ester compound of expression of being selected from,
In the formula,
X represents oxygen atom or sulphur atom,
Y represent oxygen atom or sulphur atom ,-S (CH
2)
nGroup that S-represents or singly-bound, wherein, n is 1 or 2,
R
1Expression C
1-C
6Alkyl,
R
2Expression C
1-C
8Alkoxyl, C
1-C
8Alkylthio group, C
1-C
4Alkyl-carbonyl-amino, C
1-C
6Alkylamino or phenyl,
R
3Expression C
1-C
8Alkyl, C
2-C
6Alkenyl, amino, phenyl, heteroaryl unsubstituted or that replaced by 1 to 4 identical or different substituting group that is selected from the following A group, or following formula (III)
In the formula, R
1, R
2The same with the definition of X
Substituent A: C
1-C
8Alkyl, C
1-C
8Alkoxyl, C
1-C
6Aliphatic acyl, C
1-C
6Alkoxy carbonyl, C
1-C
6Alkylthio group, C
1-C
6Alkylamino, two C
1-C
6Alkyl amino, C
1-C
4Alkyl sulphinyl, C
1-C
4Haloalkyl, N-C
1-C
4Alkyl-carbamoyl, N, N-two C
1-C
4Alkyl-carbamoyl, N-C
1-C
4Alkyl-N-formoxyl carbamoyl, can substituted heteroaryl, can substituted phenyl, halogen atom, nitro, cyano group, hydroxyl and acetylamino.
2. composition as claimed in claim 1, wherein, when being 1 weight portion with the fragrant pyrrole of chlorine, the total amount of one or more organophosphorus ester compounds is the 0.01-100 weight portion.
3. composition as claimed in claim 1 or 2, wherein, described organophosphorus ester compound is to be selected from following 1) to 15) at least a:
1) O-4-cyano-phenyl O, O-dimethyl disulfide phosphorothioate,
2) O-ethyl O-4-nitrobenzophenone thionic phosphonic acids phenyl ester,
3) S-benzyl O, O-diisopropyl thiophosphate,
4) O, O-dimethyl O-4-nitro--the tolyl phosphorothionate,
5) O, O-dimethyl O-4-methyl mercapto--the tolyl phosphorothionate,
6) S-α-ethoxy carbonyl benzyl O, O-Methyl disulfide substituted phosphate,
7) O, O, O ', O '-tetraethyl S, S '-di-2-ethylhexylphosphine oxide (phosphorodithioate),
8) O, O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothionate,
9) O, O-dimethyl O-3,5,6-trichloro-2-pyridyl phosphorothionate,
10) O-ethyl O-4-(methyl mercapto) phenyl S-propyl disulfide substituted phosphate,
11) O, O-diethyl O-2-isopropyl-6-methylpyrimidine-4-base phosphorothionate,
12) O, O-diethyl O-(2,3-dihydro-3-oxo-2-phenyl-6-pyridazinyl) phosphorothionate,
13) O-(2,4 dichloro benzene base) O-ethyl S-propyl disulfide substituted phosphate,
14) the S-6-chloro-2,3-dihydro-2-oxo--1, and 3-benzoxazole-3-ylmethyl O, the O-diethyl phosphorothioate,
15) S-1, two (ethoxy carbonyl) ethyl O of 2-, O-Methyl disulfide substituted phosphate.
4. composition as claimed in claim 1, wherein, when being 1 weight portion with the fragrant pyrrole of chlorine, one or more total amounts that are selected from the organophosphorus ester compound of the described compound of claim 3 are the 0.01-100 weight portion.
5. composition as claimed in claim 1, wherein, when being 1 weight portion with the fragrant pyrrole of chlorine, one or more total amounts that are selected from the organophosphorus ester compound of the described compound of claim 3 are the 0.5-20 weight portion.
6. the preparation of compositions method of claim 1, it comprises mixes acceptable solid on active component and the agriculture and garden or liquid-carrier.
7. method as claimed in claim 6, wherein, active component is that the fragrant pyrrole of chlorine and one or more are selected from the organophosphorus compounds of the described compound of claim 3.
8. method as claimed in claim 7, wherein, when being 1 weight portion with the fragrant pyrrole of chlorine, one or more total amounts that are selected from the organophosphorus ester compound of the described compound of claim 3 are the 0.5-20 weight portion.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33086696A JP4055022B2 (en) | 1996-12-11 | 1996-12-11 | Insecticides and acaricides |
| JP330866/1996 | 1996-12-11 | ||
| JP330866/96 | 1996-12-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1241115A true CN1241115A (en) | 2000-01-12 |
| CN1099235C CN1099235C (en) | 2003-01-22 |
Family
ID=18237400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97180397A Expired - Fee Related CN1099235C (en) | 1996-12-11 | 1997-12-08 | Insecticidal and miticidal compositions |
Country Status (19)
| Country | Link |
|---|---|
| US (2) | US6316430B1 (en) |
| EP (1) | EP0957685B1 (en) |
| JP (1) | JP4055022B2 (en) |
| KR (1) | KR100466741B1 (en) |
| CN (1) | CN1099235C (en) |
| AR (1) | AR012543A1 (en) |
| AT (1) | ATE213907T1 (en) |
| AU (1) | AU723488B2 (en) |
| BR (1) | BR9713912B1 (en) |
| CA (1) | CA2268721A1 (en) |
| DE (1) | DE69710924D1 (en) |
| ES (1) | ES2174305T3 (en) |
| ID (1) | ID22288A (en) |
| IL (1) | IL130277A (en) |
| NZ (1) | NZ336095A (en) |
| TR (1) | TR199901300T2 (en) |
| TW (1) | TW408007B (en) |
| WO (1) | WO1998025461A1 (en) |
| ZA (1) | ZA9711126B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387130C (en) * | 2006-01-17 | 2008-05-14 | 浙江升华拜克生物股份有限公司 | Compound insecticide contg. fipronil |
| CN101406189B (en) * | 2008-10-17 | 2012-02-29 | 广西田园生化股份有限公司 | Aqueous emulsion containing chlorfenapyr and preparation method thereof |
| CN101647468B (en) * | 2009-07-31 | 2013-02-13 | 深圳诺普信农化股份有限公司 | Pesticide combination containing capillary |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE243934T1 (en) | 1999-03-12 | 2003-07-15 | Basf Ag | SYNERGISTIC INSECTICIDE COMPOSITIONS |
| CN105246074A (en) | 2015-10-29 | 2016-01-13 | 小米科技有限责任公司 | Method and device for establishing connections |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL100110A0 (en) * | 1990-12-26 | 1992-08-18 | American Cyanamid Co | Insecticidal and synergistic miticidal compositions |
| AU722204B2 (en) | 1995-10-31 | 2000-07-27 | Sumitomo Chemical Company, Limited | Pesticidal composition |
| JPH09227310A (en) * | 1995-12-21 | 1997-09-02 | Mitsubishi Chem Corp | Acaricide for in house dust acarid |
-
1996
- 1996-12-11 JP JP33086696A patent/JP4055022B2/en not_active Expired - Fee Related
-
1997
- 1997-12-08 ID IDW990244A patent/ID22288A/en unknown
- 1997-12-08 DE DE69710924T patent/DE69710924D1/en not_active Expired - Lifetime
- 1997-12-08 CN CN97180397A patent/CN1099235C/en not_active Expired - Fee Related
- 1997-12-08 IL IL13027797A patent/IL130277A/en not_active IP Right Cessation
- 1997-12-08 KR KR10-1999-7005137A patent/KR100466741B1/en not_active IP Right Cessation
- 1997-12-08 NZ NZ336095A patent/NZ336095A/en unknown
- 1997-12-08 ES ES97946150T patent/ES2174305T3/en not_active Expired - Lifetime
- 1997-12-08 TR TR1999/01300T patent/TR199901300T2/en unknown
- 1997-12-08 US US09/319,479 patent/US6316430B1/en not_active Expired - Lifetime
- 1997-12-08 WO PCT/JP1997/004497 patent/WO1998025461A1/en active IP Right Grant
- 1997-12-08 AT AT97946150T patent/ATE213907T1/en not_active IP Right Cessation
- 1997-12-08 AU AU51386/98A patent/AU723488B2/en not_active Ceased
- 1997-12-08 BR BRPI9713912-2A patent/BR9713912B1/en not_active IP Right Cessation
- 1997-12-08 EP EP97946150A patent/EP0957685B1/en not_active Expired - Lifetime
- 1997-12-08 CA CA002268721A patent/CA2268721A1/en not_active Abandoned
- 1997-12-09 TW TW086118533A patent/TW408007B/en active
- 1997-12-10 ZA ZA9711126A patent/ZA9711126B/en unknown
- 1997-12-11 AR ARP970105839A patent/AR012543A1/en active IP Right Grant
-
2001
- 2001-09-28 US US09/966,662 patent/US6649646B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387130C (en) * | 2006-01-17 | 2008-05-14 | 浙江升华拜克生物股份有限公司 | Compound insecticide contg. fipronil |
| CN101406189B (en) * | 2008-10-17 | 2012-02-29 | 广西田园生化股份有限公司 | Aqueous emulsion containing chlorfenapyr and preparation method thereof |
| CN101647468B (en) * | 2009-07-31 | 2013-02-13 | 深圳诺普信农化股份有限公司 | Pesticide combination containing capillary |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4055022B2 (en) | 2008-03-05 |
| WO1998025461A1 (en) | 1998-06-18 |
| IL130277A (en) | 2005-03-20 |
| AR012543A1 (en) | 2000-11-08 |
| US6649646B2 (en) | 2003-11-18 |
| KR100466741B1 (en) | 2005-01-17 |
| EP0957685B1 (en) | 2002-03-06 |
| CA2268721A1 (en) | 1998-06-18 |
| BR9713912B1 (en) | 2009-08-11 |
| NZ336095A (en) | 2000-11-24 |
| ZA9711126B (en) | 1998-06-23 |
| TW408007B (en) | 2000-10-11 |
| IL130277A0 (en) | 2000-06-01 |
| CN1099235C (en) | 2003-01-22 |
| JP2001010912A (en) | 2001-01-16 |
| TR199901300T2 (en) | 1999-08-23 |
| ES2174305T3 (en) | 2002-11-01 |
| AU723488B2 (en) | 2000-08-31 |
| DE69710924D1 (en) | 2002-04-11 |
| US6316430B1 (en) | 2001-11-13 |
| AU5138698A (en) | 1998-07-03 |
| KR20000057479A (en) | 2000-09-15 |
| BR9713912A (en) | 2000-02-29 |
| ATE213907T1 (en) | 2002-03-15 |
| ID22288A (en) | 1999-09-30 |
| EP0957685A1 (en) | 1999-11-24 |
| US20020068760A1 (en) | 2002-06-06 |
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